Poorly crystalline transition metal tungstate

ABSTRACT

A hydroprocessing catalyst has been developed. The catalyst is a poorly crystalline transition metal tungstate material or a metal sulfide decomposition product thereof. The hydroprocessing using the crystalline ammonia transition metal tungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/692,101 filed Jun. 29, 2018, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new catalyst such as a hydroprocessingcatalyst. More particularly this invention relates to a poorlycrystalline transition metal tungstate and its use as a hydroprocessingcatalyst. Hydroprocessing may include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni—Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution à l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. Acad. Sci., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻ (MoO₄)₂.H₂O,and E_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M canbe Zn²⁺, Co²⁺ or Ni²⁺.

Pezerat assigned the different phases he observed as being Φc, Φx or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, Inorg. Chem., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, Inorg. Chem., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, Inorg. Chem., 24, 4606.

The structure of Φy was not confirmed until 1996 by Ying et al. Theirinvestigation into a room temperature chimie douce synthesis techniquein the pursuit of a layered ammonium zinc molybdate led to a metastablealuminum-substituted zincite phase, prepared by the calcination of Zn/Allayered double hydroxide (Zn₄Al₂(OH)₁₂CO₃.zH₂O). See example D. Levin,S. L. Soled, J. Y. Ying, Inorg. Chem., 1996, 35, 4191-4197. Thismaterial was reacted with a solution of ammonium heptamolybdate at roomtemperature to produce a highly crystalline compound, the structure ofwhich could not be determined through conventional ab-initio methods.The material was indexed, yielding crystallographic parameters whichwere the same as that of an ammonium nickel molybdate, reported byAstier, see example M. P. Astier, G. Dji, S. Teichner, J. Ann. Chim.(Paris), 1987, 12, 337, a material belonging to a family ofammonium-amine-nickel-molybdenum oxides closely related to Pezerat'smaterials. Astier did not publish any detailed structural data on thisfamily of materials, leading to Ying et al reproducing the material tobe analyzed by high resolution powder diffraction in order to elucidatethe structure. Ying et al named this class of materials ‘layeredtransition-metal molybdates’ or LTMs.

Since the initial reports of unsupported Ni—Mo/W oxidic precursors, U.S.Pat. No. 6,156,695, there have been several reports describing materialswhich, when sulfided, claim to have enhanced hydrotreating activities.U.S. Pat. No. 6,534,437 discloses a process for preparing a mixed metalcatalyst having a powder x-ray diffraction pattern showing reflectionsat approximately 2.53 Angstroms and 1.70 angstroms. U.S. Pat. No.6,534,437 differentiates itself from U.S. Pat. No. 3,678,124 and WO9903578 based on characteristic full width half maximum line widths ofmore resolved reflections, present in WO 9903578, claiming that theinvention of U.S. Pat. No. 6,534,437 possesses a ‘differentmicrostructure’ from prior work, WO 9903578.

U.S. Pat. No. 8,722,563 describes preparing a series of catalystprecursors with compositions comprising at least one Group VI metal andone metal from Group VIII through Group X. One of the comparativeexamples described in the patent yields a comparable powder x-raydiffraction pattern to that obtained in U.S. Pat. No. 6,534,437 and isdescribed as the as-synthesized and dried hexagonal NiWO₄ catalystprecursor.

U.S. Pat. No. 7,648,941 discloses synthetic examples of a series ofdifferent bimetallic materials and states that the bulk bimetalliccatalyst of the invention has a metastable structure and further assertthat the crystalline 2θ structure of the metastable hexagonal NiW0₄phase in the preferred catalysts of the invention have latticeparameters a=2.92 Å, b=2.93 Å, and c=4.64 Å and that bulk catalyst has ametastable hexagonal structure having an X-ray diffraction pattern witha single reflection between 58 and 65°. As a point of reference, thelargest two d-spacings which can be generated in an x-ray diffractionpattern by a hexagonal cell with lattice parameters a=2.92 Å, b=2.93 Å,and c=4.64 Å are 4.64 Å and 2.53 Å.

A. Dias and V. S. T. Ciminelli, J. Eur. Ceramic. Soc, 2001, 21,2061-2065 reported on the thermodynamic calculations and modeling ofhydrothermally synthesized nickel tungstates. They present a series ofcalculated yield diagrams at various synthesis temperatures highlightingthe pH and reagent concentrations which yield NiWO₄. All theircalculations predict the formation of a nickel tungstate between pH 2and 7.5, with nickel hydroxide being the main product at higher pH's.The authors show the x-ray diffraction patterns for the samples producedat 200, 230 and 260° C. within and without their predicted yield zones.The x-ray diffraction pattern for the NiWO₄ material synthesized at 200°C. can be described as poorly crystalline and the reference asserts thatit is important to note that a crystallized material was obtained at200° C., but with extremely fine particle size indicated by broad X-raydiffraction peaks. The reference asserts this can be explained by theenergy barrier for the precipitation, which is closely related to thenature of the rate-controlling step in the dominant formation process.The reference puts forth that higher reaction temperatures acceleratethe crystallization process because of greater thermal energy toovercome the energy barrier for transformation, and a consequence,materials with higher crystallinity and/or particle size can beobtained. The reference suggests that the phase obtained at 200° C. isessentially a poorly crystalline, nano-wolframite (NiWO₄), and thisconclusion is consistent with calculated yield diagrams of thereference.

Y. Bi, H. Nie, D. Li, S. Zeng, Q. Yang and M. Li, ChemicalCommunications, 2010, 46, 7430-7432 discuss the preparation of NiWO₄nanoparticles as a promising hydrodesulfurization catalyst, stating thatall the reflections in a typical powder x-ray diffraction pattern can beindexed undisputedly to the monoclinic NiWO₄, Wolframite, phase. Thereference asserts that FIG. 1 shows the typical X-ray diffraction (XRD)pattern of the as-made sample and all reflections can be indexedundisputedly to the monoclinic NiWO₄ phase (JCPDS card 72-1189). Thereference concludes that a close examination reveals that thereflections in the XRD pattern are a little broad, indicating thecharacteristic feature of nanosized materials.

SUMMARY OF THE INVENTION

A poorly crystalline transition metal tungstate material has beenproduced and optionally sulfided, to yield an active catalyst or acatalyst precursor such as a hydroprocessing catalyst. The poorlycrystalline transition metal tungstate material has a x-ray powderdiffraction pattern showing broad peaks at 6.3, 3.6, 3.12 and 2.74 Å.The poorly crystalline transition metal tungstate material has theformula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof; m variesfrom 0.001 to 2, or from 0.01 to 1.5, or from 0.1 to 1; ‘n’ varies from0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.4 to 3, or from 0.5 to 2, orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; ‘h’ varies from 0 to m;and ‘i’ varies from 0 to m; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

Another embodiment involves a method of making a poorly crystallinetransition metal tungstate material having the formula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof; m variesfrom 0.001 to 2, or from 0.01 to 1.5, or from 0.1 to 1; ‘n’ varies from0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.4 to 3, or from 0.5 to 2, orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; ‘h’ varies from 0 to m;and ‘i’ varies from 0 to m; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 wthe method comprising of forming an aqueous reaction solution containingNH₄ ⁺, H₃O⁺ or combinations thereof and sources of M and W and reactingthe mixture together at elevated temperatures in an open or sealedvessel to generate reaction product, recovering the reaction product anddrying at a temperature from about 100° C. to about 350° C. for about 30minutes to about 48 hours to generate the poorly crystalline transitionmetal tungstate material.

Yet another embodiment involves a conversion process comprisingcontacting a sulfiding agent with a material to generate metal sulfideswhich are contacted with a feed at conversion conditions to generate atleast one product, the material comprising a poorly crystallinetransition metal tungstate material having the formula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof; m variesfrom 0.001 to 2, or from 0.01 to 1.5, or from 0.1 to 1; ‘n’ varies from0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.4 to 3, or from 0.5 to 2, orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; ‘h’ varies from 0 to m;and ‘i’ varies from 0 to m; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

Additional features and advantages of the invention will be apparentfrom the description of the invention, FIGURES and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is the x-ray powder diffraction pattern of a poorlycrystalline transition metal tungstate material prepared by the methodas described in the Examples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a poorly crystalline transition metaltungstate composition and a process for preparing the composition. Thematerial has the designation UPM-21. This composition has an empiricalformula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof; m variesfrom 0.001 to 2, or from 0.01 to 1.5, or from 0.1 to 1; ‘n’ varies from0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.4 to 3, or from 0.5 to 2, orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; ‘h’ varies from 0 to m;and ‘i’ varies from 0 to m.

The poorly crystalline transition metal tungstate composition of theinvention is characterized by having an extended network of M-O-M, whereM represents a metal, or combination of metals listed above. Thestructural units repeat itself into at least two adjacent unit cellswithout termination of the bonding. The composition can have aone-dimensional network, such as, for example, linear chains.

The poorly crystalline transition metal tungstate composition is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A.

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

The poorly crystalline transition metal tungstate composition of theinvention is further characterized by the x-ray powder diffractionpattern shown in the FIGURE.

The poorly crystalline transition metal tungstate composition can beprepared by solvothermal crystallization of a reaction mixture,typically by mixing reactive sources of tungsten with the appropriatemetal ‘M’.

Sources of M, and W include, but are not limited to, the respectivehalide, sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols,hydroxide salts, and oxides of M, or W. Specific examples of sources ofM include, but are not limited to, manganese nitrate, manganesechloride, manganese bromide, manganese sulfate, manganese carbonate,manganese sulfide, manganese hydroxide, manganese oxide, copper nitrate,copper chloride, copper bromide, copper sulfate, copper carbonate,copper acetate, copper oxalate, copper sulfide, copper hydroxide, copperoxide, zinc nitrate, zinc chloride, iron bromide, zinc sulfate, zinccarbonate, zinc acetate, zinc oxalate, zinc sulfide, zinc hydroxide,zinc oxide, and any mixture thereof. Additional specific sources includenickel chloride, nickel bromide, nickel nitrate, nickel acetate, nickelcarbonate, nickel hydroxide, cobalt chloride, cobalt bromide, cobaltnitrate, cobalt acetate, cobalt carbonate, cobalt hydroxide, cobaltsulfide, nickel chloride, cobalt oxide, nickel bromide, nickel sulfide,nickel oxide, iron acetate, iron oxalate, iron nitrate, iron chloride,iron bromide, iron sulfate, iron carbonate, iron oxalate, iron sulfide,iron oxide, magnesium chloride, vanadium chloride and any mixturethereof. Yet additional sources include, but are not limited to,tungstates and thiotungstates, such as tungsten trioxide, tungstic acid,tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate,ammonium ditungstate, sodium ditungstate, ammonium metatungstate,ammonium paratungstate, sodium ditungstate, sodium ditungstate, sodiummetatungstate, sodium paratungstate, and any mixture thereof.

Generally, the process used to prepare the composition of this inventioninvolves forming a reaction mixture wherein the components, such as forexample, Ni, W, NH₄OH and H₂O are mixed together. By way of specificexamples, a reaction mixture may be formed which in terms of molarratios of the oxides is expressed by the formula:

MO_(x):AWO_(z):B(NH₃):H₂O

where ‘M’ is selected from the group consisting of iron, cobalt, nickel,manganese, vanadium, copper, zinc, and combinations thereof, ‘x’ is anumber which satisfies the valency of ‘M’; ‘A’ represents the ratio of‘W’ relative to ‘M’ and varies from 0.4 to 3, or from 0.5 to 2, or from0.7 to 1.25; ‘z’ is a number satisfies the valency of ‘W’; ‘B’represents the molar ratio of ‘NH₃’ and may vary from 0.1 to 100, orfrom 1 to 50, or from 2.5 to 25; the molar ratio of H₂O varies from 1 to5000, or from 10 to 300, or from 20 to 100.

The reaction mixture, comprising NH₃, H₂O, or a combination thereof, andsources of M and W, is reacted at temperatures ranging from about 90° C.to about 350° C. for a period of time ranging from 30 minutes to around14 days. In one embodiment, the temperate range for the reaction is fromabout 90° C. to about 120° C. and in another embodiment the temperatureis in the range of from about 200° C. to about 250° C. In oneembodiment, the reaction time is from about 2 to about 4 hours, and inanother embodiment the reaction time is from about 4 to 7 days. Thereaction may be carried out under atmospheric pressure or in a sealedvessel under autogenous pressure. In one embodiment, the synthesis maybe conducted in an open vessel. The reaction product is then recovered.The recovery may be by evaporation of solvent, decantation, filtration,or centrifugation. Once recovered, the reaction product is dried at atemperature of from about 100° C. to about 350° C. for about 30 minutesto about 48 hours to generate the poorly crystalline transition metaltungstate material. The poorly crystalline transition metal tungstatecompositions are characterized by their x-ray powder diffraction patternas shown in Table A above and the FIGURE.

In the art of hydrothermal synthesis of metal oxides, it is well knownthat hydroxide defects occur in metal oxides made by this route, and arelocated either internally as defects or externally as a result of oftenlarge external surface areas that are at least partially hydroxylated.These nonstoichiometric amounts of hydroxide moieties additively,together with the oxide ions, account for the collective valences of themetal ions in the compositions.

In one embodiment, an intermediate may be formed before reacting thereaction mixture. The intermediate is formed by removing at least someof the NH₃, H₂O, or a combination thereof to generate the intermediatewhich may be a precipitate, or at least a portion of the reactionmixture, or both a precipitate and a portion of the reaction mixture.The intermediate is then reacted as the reaction mixture at atemperature from about 90° C. to about 350° C. for a period of fromabout 30 minutes to 14 days to generate the reaction product which isthen dried to form the poorly crystalline transition metal tungstatematerial.

Once formed, the poorly crystalline transition metal tungstate may havea binder incorporated, where the selection of binder includes but is notlimited to, anionic and cationic clays such as hydrotalcites,pyroaurite-sjogrenite-hydrotalcites, montmorillonite and related clays,kaolin, sepiolites, silicas, alumina such as (pseudo) boehomite,gibbsite, flash calcined gibbsite, eta-alumina, zirconia, titania,alumina coated titania, silica-alumina, silica coated alumina, aluminacoated silicas and mixtures thereof, or other materials generally knownas particle binders in order to maintain particle integrity. Thesebinders may be applied with or without peptization. The binder may beadded to the bulk crystalline transition metal tungstate composition,and the amount of binder may range from about 1 to about 30 wt % of thefinished catalysts or from about 5 to about 26 wt % of the finishedcatalyst. The binder may be chemically bound to the poorly crystallinetransition metal tungstate composition, or may be present in a physicalmixture with the poorly crystalline transition metal tungstatecomposition.

At least a portion of the poorly crystalline transition metal tungstate,with or without a binder, or before or after inclusion of a binder, canbe sulfided in situ in an application or pre-sulfided to form metalsulfides which in turn are used in an application as a catalyst. Thesulfidation may be conducted under a variety of sulfidation conditionssuch as through contact of the poorly crystalline transition metaltungstate with a sulfiding agent such as sulfur containing stream orfeedstream, or a gaseous mixture of H₂S/H₂, or both. The sulfidation ofthe poorly crystalline transition metal tungstate may performed atelevated temperatures, typically ranging from about 50° C. to about 600°C., or from about 150° C. to about 500° C., or from about 250° C. toabout 450° C. The materials resulting from the sulfiding step, thedecomposition products, are referred to as metal sulfides which can beused as catalysts in conversion processes. As noted above, at least aportion of the metal sulfides may be present in a mixture with at leastone binder. The sulfiding step can take place at a location remote fromother synthesis steps, remote from the location of the conversionprocess, or remote from both the location of synthesis and remote fromlocation of the conversion process.

As discussed, at least a portion of the poorly crystalline transitionmetal tungstate of this invention can be sulfided and the resultingmetal sulfides used as catalysts in conversion processes such ashydrocarbon conversion processes. Hydroprocessing is one class ofhydrocarbon conversion processes in which the crystalline mixedtransition metal tungstate, or metal sulfides derived therefrom, isuseful as a catalyst. Examples of specific hydroprocessing processes arewell known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment, a conversion process comprisescontacting the crystalline mixed transition metal tungstate with asulfiding agent to generate metal sulfides which are contacted with afeed stream at conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, preferably about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets ofthese ranges may be employed depending upon the feedstock being used.For example, when hydrotreating a typical diesel feedstock, operatingconditions may include from about 3.5 MPa to about 8.6 MPa, from about315° C. to about 410° C., from about 0.25/h to about 5/h, and from about84 Nm³ H₂/m³ to about 850 Nm³ H₂/m³ feed. Other feedstocks may includegasoline, naphtha, kerosene, gas oils, distillates, and reformate.

Any of the lines, conduits, units, devices, vessels, surroundingenvironments, zones or similar used in the process may be equipped withone or more monitoring components including sensors, measurementdevices, data capture devices or data transmission devices. Signals,process or status measurements, and data from monitoring components maybe used to monitor conditions in, around, and on process equipment.Signals, measurements, and/or data generated or recorded by monitoringcomponents may be collected, processed, and/or transmitted through oneor more networks or connections that may be private or public, generalor specific, direct or indirect, wired or wireless, encrypted or notencrypted, and/or combination(s) thereof, the specification is notintended to be limiting in this respect.

Signals, measurements, and/or data generated or recorded by monitoringcomponents may be transmitted to one or more computing devices orsystems. Computing devices or systems may include at least one processorand memory storing computer-readable instructions that, when executed bythe at least one processor, cause the one or more computing devices toperform a process that may include one or more steps. For example, theone or more computing devices may be configured to receive, from one ormore monitoring component, data related to at least one piece ofequipment associated with the process. The one or more computing devicesor systems may be configured to analyze the data. Based on analyzing thedata, the one or more computing devices or systems may be configured todetermine one or more recommended adjustments to one or more parametersof one or more processes described herein. The one or more computingdevices or systems may be configured to transmit encrypted orunencrypted data that includes the one or more recommended adjustmentsto the one or more parameters of the one or more processes describedherein.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the appended claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “Io” being the intensityof the strongest line or peak, and “I” being the intensity of each ofthe other peaks. As will be understood by those skilled in the art thedetermination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. In some of the x-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, and w, which represent very strong, strong, medium,and weak, respectively. In terms of 100(I/I₀), the above designationsare defined as:

-   -   w=0.01-15, m=15-60: s=60-80 and vs=80-100

In certain instances, the purity of a synthesized product may beassessed with reference to its x-ray powder diffraction pattern. Thus,for example, if a sample is stated to be pure, it is intended only thatthe x-ray pattern of the sample is free of lines attributable tocrystalline impurities, not that there are no amorphous materialspresent. As will be understood to those skilled in the art, it ispossible for different poorly crystalline materials to yield peaks atthe same position. If a material is composed of multiple poorlycrystalline materials, then the peak positions observed individually foreach poorly crystalline material would be observed in the resultingsummed diffraction pattern. Likewise it is possible to have some peaksappear at the same positions within different, single phase, crystallinematerials, which may be simply a reflection of a similar distance withinthe materials and not that the materials possess the same structure.

Example 1

Ammonium metatungstate hydrate (25.3 g, 0.1 moles of W) and NH₄OH (5.0g, 0.048 moles of NH₃) were thoroughly mixed together prior to theaddition of nickel nitrate hexahydrate (20 g, 0.069 moles of Ni) andzinc nitrate hexahydrate (2.3 g, 0.0077 moles). The resultant materialwas mixed thoroughly prior to being heated at 65° C. for 24 hours in asealed vessel. The resultant slurry was transferred to a ceramic dishand heated to a maximum of 250° C. for a further 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the FIGURE.

Example 2

Using a ceramic dish cobalt nitrate hexahydrate (29.1 g, 0.1 moles ofCo), ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium carbonate (30.76 g, 0.64 moles of NH₃) were mixed thoroughlybefore being heat treated for 12 hours at 150° C. with intermittentmixing. The mixture was then heat treated further at 350° C. for 24hours. The resulting product was analyzed by X-ray powder diffraction,and the X-ray powder diffraction pattern is shown in the FIGURE.

Example 3

Using a ceramic dish, nickel nitrate hexahydrate (26.1 g, 0.09 moles ofNi), ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium carbonate (8.3 g, 0.17 moles of NH₃) were added together andmixed thoroughly prior to being heated to 70° C. The mixture transformedto a green slurry which was heated further at 300° C. with intermittentmixing for a 48 hour period. The resulting product was analyzed by X-raypowder diffraction, and the X-ray powder diffraction pattern is shown inthe FIGURE.

Example 4

Nickel nitrate hexahydrate (29.75 g, 0.1 moles of Ni) and ammoniummetatungstate hydrate (17.71 g, 0.07 moles of W) and urea (10 g, 0.167moles) and DI H₂O (5 g, 0.278 moles) were mixed together in a sealedPTFE bottle. The mixture heat treated for 30 hours at 65° C. withintermittent mixing, prior to being transferred to a ceramic dish andheat treated at 300° C. The resulting product was analyzed by X-raypowder diffraction, and the X-ray powder diffraction pattern is shown inthe FIGURE.

Embodiments

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a crystalline transition metaltungstate material having the formula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof, m variesfrom 0.001 to 2; ‘n’ varies from 0.001 to 2; ‘M’ is a metal selectedfrom Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof, ‘y’ varies from0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of thecationic species present in the material; ‘h’ varies from 0 to m; and‘i’ varies from 0 to m; the material further characterized by a x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwherein the poorly crystalline transition metal tungstate material ispresent in a mixture with at least one binder and wherein the mixturecomprises up to 25 wt-% binder. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the firstembodiment in this paragraph wherein the binder is selected from thegroup consisting of silicas, aluminas, and silica-aluminas. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the first embodiment in this paragraph whereinM is nickel or zinc. An embodiment of the invention is one, any or allof prior embodiments in this paragraph up through the first embodimentin this paragraph wherein M is nickel.

A second embodiment of the invention is a method of making a poorlycrystalline transition metal tungstate material having the formula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof, m variesfrom 0.001 to 2; ‘n’ varies from 0.001 to 2; ‘M’ is a metal selectedfrom Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof; ‘y’ varies from0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of thecationic species present in the material; ‘h’ varies from 0 to m; and‘i’ varies from 0 to m; the material further characterized by a x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 wthe method comprising: forming a reaction mixture containing NH₄ ⁺, H₃O⁺or combinations thereof, and sources of M and W; reacting the mixture ata temperature of from about 90° C. and to about 350° C. in an autogenousenvironment to form a reaction product; recovering the reaction product;and drying the recovered product at a temperature from about 100° C. toabout 350° C. for about 30 minutes to about 48 hours to generate thepoorly crystalline transition metal tungstate material. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the second embodiment in this paragraph further comprisingremoving at least some of the NH₄ ⁺, H₃O⁺ or combination thereof to forman intermediate before reacting the mixture at a temperature from about90° C. to about 350° C. in an autogenous environment. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the second embodiment in this paragraph wherein the reactingis conducted from about 30 minutes to 14 days. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph wherein the recoveringis by filtration or centrifugation. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thesecond embodiment in this paragraph further comprising adding a binderto the recovered poorly crystalline transition metal tungstate material.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphwherein the binder is selected from the group consisting of aluminas,silicas, and alumina-silicas. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph further comprising decomposing therecovered poorly crystalline transition metal tungstate material bysulfidation to form metal sulfides.

A third embodiment of the invention is a conversion process comprisingcontacting a feed with a catalyst at conversion conditions to give atleast one product, the catalyst comprising a poorly crystallinetransition metal tungstate material having the formula:

A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i)

where ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof, m variesfrom 0.001 to 2; ‘n’ varies from 0.001 to 2; ‘M’ is a metal selectedfrom Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof; ‘y’ varies from0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of thecationic species present in the material; ‘h’ varies from 0 to m; and‘i’ varies from 0 to m; the material further characterized by a x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the third embodiment in this paragraphwherein the conversion process is hydroprocessing. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the third embodiment in this paragraph wherein the conversionprocess is selected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the third embodiment inthis paragraph wherein the poorly crystalline transition metal tungstatematerial, or at least a portion of the metal sulfides, or both arepresent in a mixture with at least one binder and wherein the mixturecomprises up to 25 wt-% binder. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the thirdembodiment in this paragraph further comprising at least one of: sensingat least one parameter of the process and generating a signal or datafrom the sensing; or generating and transmitting a signal; or generatingand transmitting data.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

1. A poorly crystalline transition metal tungstate material having theformula:A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i) where ‘A’ is selected fromNH₄ ⁺, H₃O⁺ or combinations thereof, m varies from 0.001 to 2; ‘n’varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn and combinations thereof, ‘y’ varies from 0.4 to 3; ‘z’ is anumber which satisfies the sum of the valency of the cationic speciespresent in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0to m; the material further characterized by a x-ray powder diffractionpattern showing peaks at the d-spacings listed in Table A: TABLE A d (Å)I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w


2. The poorly crystalline transition metal tungstate material of claim 1wherein the poorly crystalline transition metal tungstate material ispresent in a mixture with at least one binder and wherein the mixturecomprises up to 25 wt-% binder.
 3. The poorly crystalline transitionmetal tungstate material of claim 2 wherein the binder is selected fromthe group consisting of silicas, aluminas, and silica-aluminas.
 4. Thepoorly crystalline transition metal tungstate material of claim 1wherein M is nickel or zinc.
 5. The poorly crystalline transition metaltungstate material of claim 1 wherein M is nickel.
 6. A method of makinga poorly crystalline transition metal tungstate material having theformula:A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i) where ‘A’ is selected fromNH₄ ⁺, H₃O⁺ or combinations thereof, m varies from 0.001 to 2; ‘n’varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn and combinations thereof, ‘y’ varies from 0.4 to 3; ‘z’ is anumber which satisfies the sum of the valency of the cationic speciespresent in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0to m; the material further characterized by a x-ray powder diffractionpattern showing peaks at the d-spacings listed in Table A: TABLE A d (Å)I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w

the method comprising: a. forming a reaction mixture containing NH₄ ⁺,H₃O⁺ or combinations thereof, and sources of M and W; b. reacting themixture at a temperature of from about 90° C. and to about 350° C. in anautogenous environment to form a reaction product; c. recovering thereaction product; and d. drying the recovered product at a temperaturefrom about 100° C. to about 350° C. for about 30 minutes to about 48hours to generate the poorly crystalline transition metal tungstatematerial.
 7. The method of claim 6 further comprising removing at leastsome of the NH₄ ⁺, H₃O⁺ or combination thereof to form an intermediatebefore reacting the mixture at a temperature from about 90° C. to about350° C. in an autogenous environment.
 8. The method of claim 6 whereinthe reacting is conducted from about 30 minutes to 14 days.
 9. Themethod of claim 6 wherein the recovering is by filtration orcentrifugation.
 10. The method of claim 6 further comprising adding abinder to the poorly crystalline transition metal tungstate material.11. The method of claim 10 wherein the binder is selected from the groupconsisting of aluminas, silicas, and alumina-silicas.
 12. The method ofclaim 6 further comprising decomposing the poorly crystalline transitionmetal tungstate material by sulfidation to form metal sulfides.
 13. Aconversion process comprising contacting a material with a sulfidingagent to convert at least a portion of the material to a metal sulfideand contacting the metal sulfide with a feed at conversion conditions togive at least one product, the material comprising a poorly crystallinetransition metal tungstate material having the formula:A_(m)M(OH)_(n)(W)_(y)O_(z).(NH₃)_(h)(H₂O)_(i) where ‘A’ is selected fromNH₄ ⁺, H₃O⁺ or combinations thereof, m varies from 0.001 to 2; ‘n’varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn and combinations thereof, ‘y’ varies from 0.4 to 3; ‘z’ is anumber which satisfies the sum of the valency of the cationic speciespresent in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0to m; the material further characterized by a x-ray powder diffractionpattern showing peaks at the d-spacings listed in Table A: TABLE A d (Å)I/I₀ (%) 6.3 w 3.6 vs 3.12 vs 2.74 m 2.38 w


14. The process of claim 13 wherein the conversion process ishydroprocessing.
 15. The process of claim 13 wherein the conversionprocess is selected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.
 16. The process of claim 13 wherein the poorlycrystalline transition metal tungstate material, or at least a portionof the metal sulfides, or both are present in a mixture with at leastone binder and wherein the mixture comprises up to 25 wt-% binder. 17.The process of claim 13, further comprising at least one of: sensing atleast one parameter of the process and generating a signal or data fromthe sensing; or generating and transmitting a signal; or generating andtransmitting data.